CN113149686B - Carbon/carbon composite material crucible with composite ceramic layer and preparation method thereof - Google Patents
Carbon/carbon composite material crucible with composite ceramic layer and preparation method thereof Download PDFInfo
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 12
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- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
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Abstract
The invention discloses a carbon/carbon composite material crucible with a composite ceramic layer and a preparation method thereof, wherein the carbon/carbon composite material crucible consists of a carbon/carbon composite material crucible base body and the composite ceramic layer attached to the inner surface of the carbon/carbon composite material crucible base body, the thickness of the composite ceramic layer is 1-5 mm, and the composite ceramic layer comprises the following components in percentage by mass: the preparation method comprises the steps of firstly preparing a composite ceramic layer blank, then bonding the blank by using a binder, and then carbonizing and siliconizing the blank to enable the carbon/carbon composite material crucible base body and the composite ceramic layer to be integrated.
Description
Technical Field
The invention belongs to the technical field of thermal field components for monocrystalline silicon drawing furnaces, and particularly relates to a carbon/carbon composite material crucible with a composite ceramic layer and a preparation method thereof.
Background
In recent years, with the exhaustion of fossil energy and the requirement of people for energy conservation and environmental protection, the development of the photovoltaic industry is strongly promoted by the nation, and the monocrystalline silicon solar cell belongs to the most mature technology and has relatively high photoelectric conversion efficiency in the current photovoltaic technical field, so that the demand of the market for monocrystalline silicon is huge at present.
More than 80% of the monocrystalline silicon is produced by a CZ (CZ method), namely: is prepared by seed crystal drawing and forming in a single crystal silicon drawing furnace. The crucible (also called as a guide cylinder) is one of the key elements of a monocrystalline silicon thermal field system and is mainly used for controlling the axial temperature gradient of the thermal field and guiding argon flow.
The crucible used by the single crystal silicon drawing furnace is an assembly formed by a graphite piece and a carbon felt at first, but considering that the assembly has the problems of poor heat preservation effect, short service life, difficult forming of the inner/outer wall of large-size graphite and the like, and meanwhile, along with the rise of new carbon fiber reinforced materials in recent years, the crucible has the advantages of high temperature resistance, light weight, high strength and the like, so the crucible material used by the single crystal silicon drawing furnace is gradually replaced by carbon/carbon composite materials (carbon fiber reinforced matrix carbon). However, during the actual pulling process of the single crystal silicon, a certain amount of silicon vapor and some SiO gas with oxidation in the furnace can corrode the carbon fiber in the carbon/carbon composite crucible, thereby affecting the performance and service life of the crucible. Therefore, the requirements of resisting silicification corrosion and oxidation of the carbon/carbon composite material crucible are particularly important.
In order to improve the silicification corrosion resistance and oxidation resistance of the carbon/carbon composite material crucible, patent CN103553711A proposes to prepare a composite coating layer of silicon carbide coating layer/silicon nitride coating layer on the surface of a carbon/carbon composite material heat-insulating cylinder so as to effectively inhibit the erosion of silicon vapor generated after the silicon material is melted on the surface of the carbon/carbon heat-insulating cylinder, but the chemical gas permeation method for preparing silicon carbide has low deposition efficiency, complex process and higher cost in the actual production process; in addition, patent CN111848201A also proposes forming a carbon/carbon crucible with a silicon carbide coating/silicon coating on the surface of the carbon/carbon crucible by using a plasma spraying method to improve the anti-silicification corrosion capability of the carbon/carbon crucible, thereby prolonging the service life of the crucible, but considering the appearance characteristics of the crucible itself, the difficulty of uniformly spraying the silicon coating on the whole inner and outer surfaces of the crucible by using a plasma spraying technology is high, and the thickness of the SiC coating prepared by the technical scheme is too thin, so that the capability of inhibiting the erosion of silicon vapor to carbon fibers in the carbon/carbon crucible is limited.
In addition, in the process of pulling the single crystal silicon, the current single crystal silicon pulling furnace places a silicon material inside a quartz crucible, and then the quartz crucible is sleeved in a carbon/carbon composite material crucible, wherein the carbon/carbon composite material crucible is used as a support body of the quartz crucible, and simultaneously, the carbon/carbon composite material crucible plays a role of guiding argon gas flow in the single crystal silicon pulling furnace. However, considering the production environment of the single crystal silicon drawing furnace, on the one hand, the quartz crucible is softened and deformed in a high temperature state of the molten silicon; on the other hand, the gap between the quartz crucible and the C/C composite material crucible and the silicon material on the inner surface of the quartz crucible can leave a part of silicon material, which finally causes that the silicon remained on the inner surface of the quartz crucible is not easy to clean in the process of changing the silicon from the liquid state to the solid state, and simultaneously, because the silicon changes from the liquid state to the solid state and has certain volume expansion, the combination between the quartz crucible and the C/C crucible is very tight, and the next furnace can be pulled only after the old quartz crucible is broken and a new quartz crucible is replaced. Because the raw materials for producing the quartz crucible are lacked and the cost of the raw materials for producing the quartz crucible by artificial synthesis is too high, the cost of the monocrystalline silicon produced by the current monocrystalline silicon drawing furnace is high finally.
Disclosure of Invention
Aiming at the problems, the invention provides the carbon/carbon composite material crucible with the composite ceramic layer and the preparation method thereof, which can not only obviously improve the silicification corrosion resistance and the oxidation resistance of the carbon/carbon composite material crucible while meeting the mechanical strength requirement and the heat preservation effect of the crucible applied to the monocrystalline silicon drawing furnace, but also can be used as a crucible for containing silicon materials without additionally using an additional quartz crucible for containing the silicon materials; in addition, the preparation process provided by the invention is relatively simple, and large-scale industrial production is easy to realize.
The technical scheme adopted by the invention is as follows:
the invention relates to a carbon/carbon composite material crucible with a composite ceramic layer, which consists of a carbon/carbon composite material crucible base body and a composite ceramic layer attached to the inner surface of the carbon/carbon composite material crucible base body, wherein the thickness of the composite ceramic layer is 1-5 mm, and the composite ceramic layer comprises the following components in percentage by mass: 50-70% of silicon carbide, 10-40% of boron nitride and 10-20% of silicon.
The invention provides a carbon/carbon composite material crucible with a composite ceramic layer, wherein the thickness of the ceramic layer is millimeter, and the carbon/carbon composite material crucible can effectively inhibit the erosion of silicon vapor to carbon fibers in the carbon/carbon crucible. In addition, the carbon/carbon composite material crucible can directly contain silicon materials, and meanwhile, the formula of the composite ceramic layer contains a proper amount of boron nitride, so that the problem that liquid silicon and the crucible are easy to adhere to the crucible is solved.
The invention relates to a preparation method of a carbon/carbon composite material crucible with a composite ceramic layer, which comprises the following steps:
step 1
Mixing resin, boron nitride and silicon powder to obtain a mixture, carrying out hot press forming on the mixture to obtain a composite ceramic layer green body, and carrying out carbonization treatment to obtain the composite ceramic layer green body, wherein the mixture comprises the following components in percentage by mass: 40-50% of resin, 10-40% of boron nitride and 10-30% of silicon powder;
step 2
Then mixing resin and silicon nitride to obtain a binder, coating the binder on the inner surface of the carbon/carbon composite material crucible matrix, then placing the composite ceramic layer blank in the carbon/carbon composite material crucible matrix, and respectively carrying out curing and carbonization treatment to obtain the carbon/carbon composite material crucible containing the composite ceramic layer blank;
step 3
Laying a layer of silicon powder at the bottom of the carbon/carbon composite material crucible containing the composite ceramic layer blank, then placing the graphite cylinder into the carbon/carbon composite material crucible containing the composite ceramic layer blank, adding the silicon powder into the gap between the carbon/carbon composite material crucible containing the composite ceramic layer blank and the graphite cylinder, carrying out ceramic treatment, taking out the graphite cylinder, and machining to obtain the carbon/carbon composite material crucible with the composite ceramic layer.
The preparation method of the invention provides a split preparation method for the composite ceramic layer and the carbon/carbon composite material crucible matrix, which comprises the following steps: the preparation method can obtain the composite ceramic layer with enough thickness, thereby effectively inhibiting the erosion of silicon vapor to the carbon/carbon composite material crucible matrix.
In addition, the invention provides that in the process of preparing the composite ceramic layer green body, by introducing the silicon powder raw material and reasonably controlling the content of the silicon powder, the inventor finds that proper introduction of a certain amount of silicon powder into the composite ceramic layer green body can effectively promote the subsequent ceramization of the composite ceramic layer green body, and the ceramization of the composite ceramic layer green body can be ensured to have better service performance only by controlling the amount of the silicon powder within the range of 10-30%, and if the content of the silicon powder is too little, the acting force for promoting the ceramization of the composite ceramic layer green body is insufficient; if the content of the silicon powder is too much, in the process of high-temperature ceramic formation, certain volume expansion exists when silicon changes from a liquid state to a solid state, so that the compactness of the composite ceramic layer is easily adversely affected, and the service performance of the composite ceramic layer is affected.
Preferably, in step 1, the resin is selected from furan resin or phenolic resin, preferably phenolic resin; the particle size of the boron nitride is selected from 1-100 μm, preferably 5-50 μm; the particle size of the silicon powder is selected from 1-200 μm, preferably 5-100 μm.
Preferably, in the step 1, the pressure of the hot press molding is 0.2MPa to 0.8 MPa.
In the preferred scheme, in the step 1, the overall size of the outer wall of the composite ceramic layer green body is 8-12% larger than that of the inner wall of the carbon/carbon composite material crucible base body, and the thickness of the composite ceramic layer green body is 1.2-6 mm.
The outer diameter of the composite ceramic layer green body is set to be 8% -12% larger than the inner diameter of the carbon/carbon composite material crucible matrix, and after the carbonization volume shrinkage, the composite ceramic layer green body can be just placed in the carbon/carbon composite material crucible matrix and is tightly attached.
In the preferable scheme, in the step 1, the carbonization treatment temperature is 800-1000 ℃, and the treatment time is 1-3 h.
Preferably, in step 2, the resin is furan resin or phenolic resin, preferably furan resin; the silicon nitride has a particle size of 1 to 50 μm, preferably 5 to 30 μm.
Preferably, in step 2, in the binder, the mass fraction of the resin is 30% to 50%, and the mass fraction of the silicon nitride is 50% to 70%.
Preferably, in the step 2, the density of the carbon/carbon composite material crucible matrix is 1.1g/cm3～1.4g/cm3The density of the carbon/carbon composite material crucible base body is 0.2g/cm3～0.6g/cm3The carbon fiber preform is densified by CVI deposition and/or resin impregnation.
Preferably, in the step 2, the roughness Ra of the inner surface of the carbon/carbon composite material crucible base body is less than or equal to 1mm, and preferably ranges from 0.2mm to 0.8 mm.
In the actual operation process, the inner surface and the outer surface of the carbon/carbon composite material crucible base body are polished to reach the required roughness.
In a preferable scheme, in the step 2, the curing temperature is 160-220 ℃, and the curing time is 2-5 hours.
In the preferable scheme, in the step 2, the temperature of the carbonization treatment is 800-1000 ℃, the time of the carbonization treatment is 0.5-2 h, and the temperature is reduced at the speed of less than or equal to 100 ℃/h, preferably 20-80 ℃ after the carbonization treatment is finished.
Preferably, in step 3, the particle size of the silicon powder is 0.001mm to 1mm, preferably 0.2mm to 0.8 mm.
In the actual operation process, a graphite cylinder with a proper size needs to be selected, so that the amount of the added silicon powder after the silicon powder is added in the gap can be uniformly contacted with the carbon/carbon composite material crucible containing the composite ceramic layer blank.
In the preferable scheme, in the step 3, the temperature of the ceramic treatment is 1500-1800 ℃, and the heat preservation time is 30-90 min; the cooling rate is less than or equal to 170 ℃/h, preferably 50-150 ℃/h.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
compared with the prior art, the carbon/carbon composite material crucible with the composite ceramic layer has the main advantages that: 1. the problem that liquid silicon and a crucible are easy to adhere to the crucible can be solved by introducing the boron nitride component into the composite ceramic layer and reasonably controlling the boron nitride component, so that the difficulty of cleaning residual silicon materials on the inner surface of the crucible is reduced, and meanwhile, the thermal expansion coefficient of the whole composite ceramic layer can be effectively reduced by properly introducing the boron nitride into the composite ceramic layer, so that the problem that the thermal expansion coefficient of the composite ceramic layer is not matched with that of the carbon/carbon composite material crucible is solved; 2. an interface bonding layer consisting of silicon nitride, silicon carbide and silicon is formed by adopting a bonding agent consisting of resin, silicon nitride and silicon, so that the compact bonding between the composite ceramic layer and the carbon/carbon composite material crucible can be realized, and meanwhile, a transition layer between the carbon/carbon composite material crucible and the composite ceramic layer is formed by reasonably optimizing the proportion of each component in the bonding layer, so that the mismatching force generated by the inconsistency of the thermal expansion coefficients between the composite ceramic layer and the carbon/carbon composite material crucible is further relieved; 3. the composite ceramic layer provided by the invention has the advantages that the preparation process is simple, the price of the required raw materials is low, the quartz crucible in the existing monocrystalline silicon drawing furnace can be omitted from the prepared crucible with the composite ceramic layer, the raw material cost of monocrystalline silicon production is reduced, and meanwhile, the production efficiency is greatly improved.
Description of the drawings:
FIG. 1 is a schematic structural view of a carbon/carbon composite crucible having a composite ceramic layer according to the present invention;
FIG. 2 is a schematic structural view of a carbon/carbon composite crucible bond containing a composite ceramic layer green body according to the present invention;
description of reference numerals:
11. the carbon/carbon composite material crucible I, 12 is compounded with a ceramic layer;
21. the carbon/carbon composite material crucible II, 22, the bonding layer, 23 and the composite ceramic layer blank;
24. 25 parts of graphite cylinder and silicon powder;
the specific implementation mode is as follows:
the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
As shown in fig. 1, the carbon/carbon composite crucible with composite ceramic layer of the present invention comprises a carbon/carbon composite crucible base body (11) and composite ceramic layers (12) respectively attached to the inner surfaces thereof, and the specific preparation steps are as follows:
step 1, preparation of carbon fiber preform
According to the shape and size requirements of the required crucible, adopting a preparation method of a conventional carbon fiber preform integral felt, alternately stacking the non-woven cloth and the net layer, and then preparing the non-woven cloth and the net layer in a needling manner to obtain the carbon fiber preform integral felt with the density of 0.2g/cm3The carbon fiber preform of (1);
step 2, densifying the carbon fiber preform
Densifying the carbon fiber preform obtained in the step 1 by adopting a Chemical Vapor Infiltration (CVI) mode and taking propylene as a gas source for chemical vapor deposition until the density is 1.1g/cm3The carbon/carbon composite of (a);
step 3, machining treatment
Mechanically polishing the carbon/carbon composite material obtained in the step 2 to obtain a carbon/carbon composite material crucible with the surface roughness Ra of 0.2 mm;
step 4, preparing a composite ceramic layer green body
Selecting 45 mass percent of phenolic resin, 10 mass percent of boron nitride (granularity is 5 mu m) and 30 mass percent of silicon powder (granularity is 100 mu m) as raw materials, uniformly mixing the raw materials, pouring the raw materials into a mould, and adopting a hot-press forming mode, wherein the forming pressure is 0.2MPa, so that the overall size of the outer wall of the obtained composite ceramic layer green body is 10 percent larger than the overall size of the inner wall of the carbon/carbon composite material crucible, and the thickness of the composite ceramic layer green body is 3.5 mm;
step 5, carbonizing the composite ceramic layer green body;
putting the composite ceramic layer green body prepared in the step 4 into a carbonization furnace for carbonization treatment, wherein the carbonization temperature is 800 ℃, and the carbonization time is 3 hours, and finally obtaining the composite ceramic layer green body;
step 6, bonding the composite ceramic layer blank with a carbon/carbon composite material crucible;
the method comprises the steps of coating a binding agent consisting of furan resin and silicon nitride (the granularity is 1 mu m) (the mass ratio is 30%: 70%) on an interface to be bound of a composite ceramic layer blank and a carbon/carbon composite crucible, then placing the composite ceramic layer blank in the carbon/carbon composite crucible to ensure that the two interfaces are bound together through the binding agent, and finally placing the binding body at the temperature of 160 ℃ for curing for 5 hours to obtain the carbon/carbon composite crucible binding body with the composite ceramic layer blank.
Step 7, carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank;
carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank obtained in the step 6 again, wherein the temperature of the carbonization treatment is 800 ℃, the time of the carbonization treatment is 2 hours, and the cooling rate is controlled to be 80 ℃/h after the carbonization treatment is finished;
step 8, high-temperature ceramic treatment of the composite ceramic layer blank
Selecting pure silicon powder to carry out high-temperature ceramic treatment on the composite ceramic layer blank in the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank after carbonization treatment in the step 7, specifically, as shown in figure 2, firstly, paving a layer of silicon powder at the bottom of the ceramic layer blank (23) in a reciprocating manner, then placing the graphite cylinder (24) into the composite ceramic layer blank (23), then adding the silicon powder into a gap between the ceramic layer blank (23) and the graphite cylinder (24) in a reciprocating manner, reasonably controlling the size of the gap between the bonding body and the graphite cylinder to ensure that the added silicon powder can be uniformly contacted with the composite ceramic layer blank, and finally carrying out high-temperature ceramic treatment. In the high-temperature ceramic process, the temperature of the high-temperature ceramic is 1500 ℃, the heat preservation time is 90min, wherein the cooling rate is 150 ℃/h after the ceramic process is finished;
step 9, machining treatment
And (3) performing machining treatment on the inner surface of the carbon/carbon composite material crucible bonding body with the composite ceramic layer green body subjected to the high-temperature ceramic treatment in the step (8), and finally obtaining the carbon/carbon composite material crucible with the composite ceramic layer (the silicon carbide accounts for 70%, the boron nitride accounts for 10% and the silicon accounts for 20%).
Comparative example 1
The specific preparation steps of the carbon/carbon composite material crucible with the composite ceramic layer are as in example 1, except that in comparative example 1, boron nitride is not introduced when the composite ceramic layer green body is prepared in step 4, phenolic resin and silicon powder are directly used as raw materials for preparing the composite ceramic layer green body, and other preparation conditions are the same as those in example 1.
Example 2
Step 1, preparation of carbon fiber preform
According to the shape and size requirements of the required crucible, adopting a preparation method of a conventional carbon fiber preform integral felt, alternately stacking the non-woven cloth and the net layer, and then preparing the non-woven cloth and the net layer in a needling manner to obtain the carbon fiber preform integral felt with the density of 0.6g/cm3The carbon fiber preform of (1);
step 2, densifying the carbon fiber preform
Firstly, adopting a furan resin impregnation mode to perform impregnation-curing and carbonization treatment on the carbon fiber preform, then adopting a Chemical Vapor Infiltration (CVI) mode, taking propylene as a gas source of chemical vapor deposition, densifying the carbon fiber preform obtained in the step 1 until the density is 1.4g/cm3The carbon/carbon composite of (a);
step 3, machining treatment
Mechanically polishing the carbon/carbon composite material obtained in the step 2 to obtain a carbon/carbon composite material crucible with the surface roughness Ra of 0.8 mm;
step 4, preparing a composite ceramic layer green body
Selecting 40% by mass of phenolic resin, 40% by mass of boron nitride (with the granularity of 50 microns) and 20% by mass of silicon powder (with the granularity of 5 microns) as raw materials, uniformly mixing the raw materials, pouring the raw materials into a mould, and adopting a hot-press forming mode, wherein the forming pressure is 0.8MPa, so that the overall size of the outer wall of the obtained composite ceramic layer green body is 8% larger than that of the inner wall of the carbon/carbon composite material crucible, and the thickness of the composite ceramic layer green body is 1.2 mm;
step 5, carbonizing the composite ceramic layer green body;
putting the composite ceramic layer green body prepared in the step 4 into a carbonization furnace for carbonization treatment, wherein the carbonization temperature is 1000 ℃, and the carbonization time is 1 hour, and finally obtaining the composite ceramic layer green body;
step 6, bonding the composite ceramic layer blank with a carbon/carbon composite material crucible;
the method comprises the steps of coating a binding agent consisting of furan resin and silicon nitride (the granularity is 50 mu m) (the mass ratio is 50%: 50%) on an interface to be bound of a composite ceramic layer blank and a carbon/carbon composite crucible, then placing the composite ceramic layer blank in the carbon/carbon composite crucible to ensure that the two interfaces are bound together through the binding agent, and finally placing the binding body at 220 ℃ for curing for 2 hours to obtain the carbon/carbon composite crucible binding body with the composite ceramic layer blank.
Step 7, carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank;
carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank obtained in the step 6 again, wherein the temperature of the carbonization treatment is 1000 ℃, the time of the carbonization treatment is 0.5 hour, and the cooling rate is controlled to be 20 ℃/h after the carbonization treatment is finished;
step 8, high-temperature ceramic treatment of the composite ceramic layer blank
Selecting pure silicon powder to carry out high-temperature ceramic treatment on the composite ceramic layer blank in the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank after carbonization treatment in the step 7, specifically, as shown in figure 2, firstly, paving a layer of silicon powder at the bottom of the ceramic layer blank (23) in a reciprocating manner, then placing the graphite cylinder (24) into the composite ceramic layer blank (23), then adding the silicon powder into a gap between the ceramic layer blank (23) and the graphite cylinder (24) in a reciprocating manner, reasonably controlling the size of the gap between the bonding body and the graphite cylinder to ensure that the added silicon powder can be uniformly contacted with the composite ceramic layer blank, and finally carrying out high-temperature ceramic treatment. In the high-temperature ceramic process, the temperature of the high-temperature ceramic is 1800 ℃ and the heat preservation time is 30min, wherein the cooling rate is 50 ℃/h after the ceramic process is finished;
step 9, machining treatment
And (3) performing machining treatment on the inner surface of the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank subjected to the high-temperature ceramic treatment in the step (8), and finally obtaining the carbon/carbon composite material crucible with the composite ceramic layer (the mass ratio of silicon carbide is 50%, the mass ratio of boron nitride is 30% and the mass ratio of silicon is 20%).
Comparative example 2
A carbon/carbon composite crucible having a composite ceramic layer and a method for preparing the same, the method comprising the following steps of example 2, except that in comparative example 2, the binder used in step 6 comprises the following components in a mass ratio of furan resin to silicon nitride: 20%: 80%, other preparation conditions were the same as in example 2.
Example 3
Step 1, preparation of carbon fiber preform
According to the shape and size requirements of the required crucible, adopting a conventional preparation method of the carbon fiber preform integral felt, alternately stacking the non-woven cloth and the net-shaped layer, and preparing the non-woven cloth and the net-shaped layer in a needling manner to obtain the carbon fiber preform integral felt with the density of 0.4g/cm3The carbon fiber preform of (1);
step 2, densifying the carbon fiber preform
Firstly, adopting a furan resin impregnation mode to perform impregnation-curing and carbonization treatment on the carbon fiber preform, then adopting a Chemical Vapor Infiltration (CVI) mode, taking propylene as a gas source of chemical vapor deposition, densifying the carbon fiber preform obtained in the step 1 until the density is 1.25g/cm3The carbon/carbon composite of (a);
step 3, machining treatment
Mechanically polishing the carbon/carbon composite material obtained in the step 2 to obtain a carbon/carbon composite material crucible with the surface roughness Ra of 0.5 mm;
step 4, preparing a composite ceramic layer green body
Selecting 50% by mass of phenolic resin, 25% by mass of boron nitride (the granularity is 27 microns) and 25% by mass of silicon powder (the granularity is 52 microns) as raw materials, uniformly mixing the raw materials, pouring the raw materials into a mould, adopting a hot-press forming mode, wherein the forming pressure is 0.5MPa, and finally ensuring that the overall size of the outer wall of the obtained composite ceramic layer green body is 12% larger than that of the inner wall of the carbon/carbon composite material crucible, and the thickness of the composite ceramic layer green body is 6 mm;
step 5, carbonizing the composite ceramic layer green body;
putting the composite ceramic layer green body prepared in the step 4 into a carbonization furnace for carbonization treatment, wherein the carbonization temperature is 900 ℃, and the carbonization time is 2 hours, and finally obtaining the composite ceramic layer green body;
step 6, bonding the composite ceramic layer blank with a carbon/carbon composite material crucible;
the method comprises the steps of coating a binding agent consisting of furan resin and silicon nitride (the granularity is 25 mu m) (the mass ratio is 40%: 60%) on an interface to be bound of a composite ceramic layer blank and a carbon/carbon composite crucible, then placing the composite ceramic layer blank in the carbon/carbon composite crucible to ensure that the two interfaces are bound together through the binding agent, and finally placing the binding body at 190 ℃ for curing for 3.5 hours to obtain the carbon/carbon composite crucible binding body with the composite ceramic layer blank.
Step 7, carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank;
carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank obtained in the step 6 again, wherein the temperature of the carbonization treatment is 900 ℃, the time of the carbonization treatment is 1.25 hours, and the cooling rate is controlled to be 50 ℃/h after the carbonization treatment is finished;
step 8, high-temperature ceramic treatment of the composite ceramic layer blank
Selecting pure silicon powder to carry out high-temperature ceramic treatment on the composite ceramic layer blank in the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank after carbonization treatment in the step 7, specifically, as shown in fig. 2, firstly, paving a layer of silicon powder at the bottom of the ceramic layer blank (23) in a reciprocating manner, then, placing the graphite cylinder (24) into the composite ceramic layer blank (23), then, adding the silicon powder into a gap between the ceramic layer blank (23) and the graphite cylinder (24) in a reciprocating manner, reasonably controlling the size of the gap between the bonding body and the graphite cylinder to ensure that the added silicon powder can be uniformly contacted with the composite ceramic layer blank, and finally, carrying out high-temperature ceramic treatment. In the high-temperature ceramic process, the temperature of the high-temperature ceramic is 1650 ℃, the heat preservation time is 60min, wherein the cooling rate is 100 ℃/h after the ceramic process is finished;
step 9, machining treatment
And (3) performing machining treatment on the inner surface of the carbon/carbon composite material crucible bonding body with the composite ceramic layer green body subjected to the high-temperature ceramic treatment in the step (8), and finally obtaining the carbon/carbon composite material crucible with the composite ceramic layer (the silicon carbide accounts for 60%, the boron nitride accounts for 20% and the silicon accounts for 20%).
Comparative example 3
A carbon/carbon composite crucible having a composite ceramic layer and a method for preparing the same, the method comprising the following steps of example 3, except that in comparative example 3, the binder used in step 6 comprises the following components in a mass ratio of furan resin to silicon nitride: 60%: 40% and the other preparation conditions were the same as in example 3.
Example 4
Step 1, preparation of carbon fiber preform
According to the shape and size requirements of the required crucible, adopting a preparation method of a conventional carbon fiber preform integral felt, alternately stacking the non-woven cloth and the net layer, and then preparing the non-woven cloth and the net layer in a needling manner to obtain the carbon fiber preform integral felt with the density of 0.3g/cm3The carbon fiber preform of (1);
step 2, densifying the carbon fiber preform
Directly adopting a Chemical Vapor Infiltration (CVI) mode, taking propylene as a gas source of chemical vapor deposition, densifying the carbon fiber preform obtained in the step 1 until the density is 1.2g/cm3The carbon/carbon composite of (a);
step 3, machining treatment
Mechanically polishing the carbon/carbon composite material obtained in the step 2 to obtain a carbon/carbon composite material crucible with the surface roughness Ra of 0.3 mm;
step 4, preparing a composite ceramic layer green body
Selecting 43 mass percent of phenolic resin, 32 mass percent of boron nitride (with the granularity of 16 mu m) and 25 mass percent of silicon powder (with the granularity of 75 mu m) as raw materials, uniformly mixing the raw materials, pouring the raw materials into a mould, adopting a hot-press forming mode, wherein the forming pressure is 0.3MPa, and finally ensuring that the overall size of the outer wall of the obtained composite ceramic layer green body is 9 percent larger than that of the inner wall of the carbon/carbon composite material crucible, and the thickness of the composite ceramic layer green body is 2.6 mm;
step 5, carbonizing the composite ceramic layer green body;
putting the composite ceramic layer green body prepared in the step 4 into a carbonization furnace for carbonization treatment, wherein the carbonization temperature is 850 ℃ and the carbonization time is 2.5 hours, and finally obtaining the composite ceramic layer green body;
step 6, bonding the composite ceramic layer blank with a carbon/carbon composite material crucible;
the bonding agent consisting of furan resin and silicon nitride (the granularity is 14 mu m) (the mass ratio is 35 percent: 65 percent) is adopted, the bonding agent is coated on the interface to be bonded between the composite ceramic layer blank and the carbon/carbon composite material crucible, then the composite ceramic layer blank is placed in the carbon/carbon composite material crucible to ensure that the two interfaces are bonded together through the bonding agent, and finally the bonding body is placed at the temperature of 170 ℃ to be cured for 4 hours, so that the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank is obtained.
Step 7, carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank;
carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank obtained in the step 6 again, wherein the temperature of the carbonization treatment is 850 ℃, the time of the carbonization treatment is 1.5 hours, and the cooling rate is controlled to be 35 ℃/h after the carbonization treatment is finished;
step 8, high-temperature ceramic treatment of the composite ceramic layer blank
Selecting pure silicon powder to carry out high-temperature ceramic treatment on the composite ceramic layer blank in the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank after carbonization treatment in the step 7, specifically, as shown in fig. 2, firstly, paving a layer of silicon powder at the bottom of the ceramic layer blank (23) in a reciprocating manner, then, placing the graphite cylinder (24) into the composite ceramic layer blank (23), then, adding the silicon powder into a gap between the ceramic layer blank (23) and the graphite cylinder (24) in a reciprocating manner, reasonably controlling the size of the gap between the bonding body and the graphite cylinder to ensure that the added silicon powder can be uniformly contacted with the composite ceramic layer blank, and finally, carrying out high-temperature ceramic treatment. In the high-temperature ceramic process, the temperature of the high-temperature ceramic is 1580 ℃, the heat preservation time is 75min, wherein the cooling rate is 125 ℃/h after the ceramic process is finished;
step 9, machining treatment
And (3) performing machining treatment on the inner surface of the carbon/carbon composite material crucible bonding body with the composite ceramic layer green body subjected to the high-temperature ceramic treatment in the step (8), and finally obtaining the carbon/carbon composite material crucible with the composite ceramic layer (55% by mass of silicon carbide, 25% by mass of boron nitride and 20% by mass of silicon).
Comparative example 4
The specific preparation steps of the carbon/carbon composite material crucible with the composite ceramic layer are as in example 4, except that in comparative example 4, the raw material for preparing the composite ceramic layer green body in step 4 does not introduce silicon powder, but directly adopts two raw materials of resin and boron nitride as the raw materials for preparing the composite ceramic layer green body, and other preparation conditions are the same as those in example 4.
Example 5
Step 1, preparation of carbon fiber preform
According to the shape and size requirements of the required crucible, adopting a preparation method of a conventional carbon fiber preform integral felt, alternately stacking the non-woven cloth and the net layer, and then preparing the non-woven cloth and the net layer in a needling manner to obtain the carbon fiber preform integral felt with the density of 0.5g/cm3The carbon fiber preform of (1);
step 2, densifying the carbon fiber preform
Firstly, adopting a mode of impregnating furan resin to carry out carbon fiber preformImpregnating, curing and carbonizing, and then densifying the carbon fiber preform obtained in the step 1 by using propylene as a gas source for chemical vapor deposition in a Chemical Vapor Infiltration (CVI) mode until the density is 1.33g/cm3The carbon/carbon composite of (a);
step 3, machining treatment
Mechanically polishing the carbon/carbon composite material obtained in the step 2 to obtain a carbon/carbon composite material crucible with the surface roughness Ra of 0.7 mm;
step 4, preparing a composite ceramic layer green body
Selecting 48 mass percent of phenolic resin, 22 mass percent of boron nitride (with the granularity of 35 mu m) and 30 mass percent of silicon powder (with the granularity of 25 mu m) as raw materials, uniformly mixing the raw materials, pouring the raw materials into a mould, and adopting a hot-press forming mode to form the composite ceramic layer green body with the forming pressure of 0.7MPa, wherein the integral size of the outer wall of the obtained composite ceramic layer green body is 11 percent larger than that of the inner wall of the carbon/carbon composite material crucible, and the thickness of the composite ceramic layer green body is 4.7 mm;
step 5, carbonizing the composite ceramic layer green body;
putting the composite ceramic layer green body prepared in the step 4 into a carbonization furnace for carbonization treatment, wherein the carbonization temperature is 950 ℃, and the carbonization time is 1.5 hours, and finally obtaining the composite ceramic layer green body;
step 6, bonding the composite ceramic layer blank with a carbon/carbon composite material crucible;
the method comprises the steps of coating a binding agent consisting of furan resin and silicon nitride (the granularity is 22 mu m) (the mass ratio is 45% to 55%) on an interface to be bound of a composite ceramic layer blank and a carbon/carbon composite material crucible, then placing the composite ceramic layer blank in the carbon/carbon composite material crucible to ensure that the two interfaces are bound together through the binding agent, and finally placing the binding body at the temperature of 210 ℃ for curing for 2.5 hours to obtain the carbon/carbon composite material crucible binding body with the composite ceramic layer blank.
Step 7, carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank;
carbonizing the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank obtained in the step 6 again, wherein the temperature of the carbonization treatment is 950 ℃, the time of the carbonization treatment is 0.8 hour, and the cooling rate is controlled to be 65 ℃/h after the carbonization treatment is finished;
step 8, high-temperature ceramic treatment of the composite ceramic layer blank
Selecting pure silicon powder to carry out high-temperature ceramic treatment on the composite ceramic layer blank in the carbon/carbon composite material crucible bonding body with the composite ceramic layer blank after carbonization treatment in the step 7, specifically, as shown in fig. 2, firstly, paving a layer of silicon powder at the bottom of the ceramic layer blank (23) in a reciprocating manner, then, placing the graphite cylinder (24) into the composite ceramic layer blank (23), then, adding the silicon powder into a gap between the ceramic layer blank (23) and the graphite cylinder (24) in a reciprocating manner, reasonably controlling the size of the gap between the bonding body and the graphite cylinder to ensure that the added silicon powder can be uniformly contacted with the composite ceramic layer blank, and finally, carrying out high-temperature ceramic treatment. In the high-temperature ceramic process, the temperature of the high-temperature ceramic is 1720 ℃ and the heat preservation time is 45min, wherein the cooling rate is 75 ℃/h after the ceramic process is finished;
step 9, machining treatment
And (3) performing machining treatment on the inner surface of the carbon/carbon composite material crucible bonding body with the composite ceramic layer green body subjected to the high-temperature ceramic treatment in the step (8), and finally obtaining the carbon/carbon composite material crucible with the composite ceramic layer (the silicon carbide accounts for 65%, the boron nitride accounts for 20% and the silicon accounts for 15%).
Comparative example 5
The specific preparation steps of the carbon/carbon composite material crucible with the composite ceramic layer are as in example 5, except that in the high-temperature ceramic process in the step 8, silicon powder is not additionally added, but the content of the silicon powder is properly increased directly in the process of preparing the composite ceramic layer green body, and the raw material components for preparing the composite ceramic layer green body respectively have the following mass ratios: 40% of resin: boron nitride 20%: 40% of silicon powder, and the other preparation conditions were the same as those in example 5.
The above examples and comparative examples as obtained carbon/carbon composite crucibles with composite ceramic layers were subjected to performance test analysis, comprising: shear strength between the ceramized composite ceramic layer and the carbon/carbon composite material crucible) and rockwell hardness value test of the composite ceramic layer, and in addition, the average service life of monocrystalline silicon straightening production is statistically analyzed under the condition that the carbon/carbon composite material with the composite ceramic layer is used as a guide cylinder and a crucible for containing silicon materials, and the obtained test results are shown in the following table 1:
TABLE 1
| Shear strength (MPa) | Average service life (moon) | Rockwell Hardness (HRL) | |
| Example 1 | 27.5 | 10 | 126.5 |
| Comparative example 1 | 25.6 | 3 | 124.2 |
| Example 2 | 21.7 | 7 | 121.4 |
| Comparative example 2 | / | / | 121.4 |
| Example 3 | 23.4 | 12 | 125.2 |
| Comparative example 3 | / | / | 125.2 |
| Example 4 | 22.8 | 9 | 122.8 |
| Comparative example 4 | 6.7 | 2 | 102.4 |
| Example 5 | 24.3 | 11 | 126.1 |
| Comparative example 5 | / | / | 42.5 |
From table 1, it can be found that the average service life of the carbon/carbon composite material crucible, which is used as both a guide cylinder crucible and a silicon material containing crucible, can be effectively prolonged by introducing boron nitride into the composite ceramic layer, mainly because the introduction of boron nitride can reduce the bonding strength between liquid silicon and the inner wall of the crucible, reduce the damage to the composite ceramic layer caused by cleaning the inner wall of the crucible after the pulling of monocrystalline silicon is completed each time, and thus prolong the service life of the carbon/carbon composite material crucible; the mismatching force between the composite ceramic layer and the carbon/carbon composite material crucible is optimized by reasonably controlling the component proportion in the intermediate transition layer, and as can be seen from a comparative example 2 and a comparative example 3 in a table 1, when the content of furan resin in the binder component is too low, the viscosity of the prepared binder slurry is too thick, the operation is not easy to perform in the implementation of the binding process, and a binding body of the carbon/carbon composite material crucible and a composite ceramic layer blank is easy to fall off in the carbonization process; however, when the furan resin content in the binder component is too high, the volume shrinkage in the carbonization process is too large, and the separation between the carbon/carbon composite material crucible and the composite ceramic layer green body is easily caused, so that the shear strength between the carbon/carbon composite material crucible and the composite ceramic layer in comparative examples 2 and 3 cannot be characterized; in addition, from the rockwell hardness values in examples 4 and 5 and comparative examples 4 and 5, it can be found that when a certain amount of silicon powder is properly introduced during the preparation of the composite ceramic layer green body, the ceramization of the composite ceramic layer green body can be promoted, so that the rockwell hardness is high, so that the rockwell hardness value of example 4 is higher than that of comparative example 4, the composite ceramic layer with high ceramization degree can show better performance and longer service life, but if more silicon powder is directly added during the preparation of the composite ceramic layer green body, and no additional silicon powder is added in the high-temperature ceramization process as a infiltrant, from comparative example 5, the composite ceramic layer is not easily ceramized, mainly because the silicon changes from a liquid state to a solid state during the high-temperature ceramization process, so that the volume expansion is easily caused, and the compactness of the composite ceramic layer is affected, the Rockwell hardness value of the ceramic composite ceramic layer is low, and at the same time, the resin carbon in the ceramic composite layer is not completely silicified, so the Rockwell hardness value of the ceramic composite layer is also influenced.
Under the normal condition at present, a single-crystal silicon drawing furnace needs about 1 month for one work flow, a quartz crucible (about 5000 yuan/crucible) needs to be consumed for each work flow, and the average service life of the carbon/carbon composite material crucible applied to the single-crystal silicon drawing furnace is 5-8 months, namely: according to the calculation of 8 months of the maximum service life of the current carbon/carbon composite material crucible, 8 quartz crucibles (at least 4 ten thousand yuan in total) are consumed in the life cycle of each carbon/carbon composite material crucible. At this time, it can be seen from the table that the service life of the carbon/carbon composite crucible having the composite ceramic layer can be at least 8 months or more, that is: on the premise of meeting the use requirement of the monocrystalline silicon drawing furnace, the cost of at least 8 quartz crucibles can be saved, so that the carbon/carbon composite material crucible with the composite ceramic layer provided by the invention can greatly reduce the cost of monocrystalline silicon production.
The above description specifically describes a carbon/carbon composite crucible having a composite ceramic layer, which can be applied to the field of thermal field crucibles, etc., but the present invention is not limited by the above description, and therefore, any improvements, equivalent modifications, substitutions, etc., which are made according to the technical gist of the present invention, fall within the scope of protection of the present invention.
Claims (9)
1. A preparation method of a carbon/carbon composite material crucible with a composite ceramic layer is characterized by comprising the following steps:
step 1
Mixing resin, boron nitride and silicon powder to obtain a mixture, carrying out hot press forming on the mixture to obtain a composite ceramic layer green body, and carrying out carbonization treatment to obtain the composite ceramic layer green body, wherein the mixture comprises the following components in percentage by mass: 40-50% of resin, 10-40% of boron nitride and 10-30% of silicon powder;
step 2
Then mixing resin and silicon nitride to obtain a binder, coating the binder on the inner surface of the carbon/carbon composite material crucible matrix, then placing the composite ceramic layer blank in the carbon/carbon composite material crucible matrix, and respectively carrying out curing and carbonization treatment to obtain the carbon/carbon composite material crucible containing the composite ceramic layer blank;
step 3
Laying a layer of silicon powder at the bottom of a carbon/carbon composite material crucible containing a composite ceramic layer blank, then placing a graphite cylinder into the carbon/carbon composite material crucible containing the composite ceramic layer blank, adding the silicon powder into a gap between the carbon/carbon composite material crucible containing the composite ceramic layer blank and the graphite cylinder, carrying out ceramic treatment, taking out the graphite cylinder, and machining to obtain the carbon/carbon composite material crucible with the composite ceramic layer;
the carbon/carbon composite material crucible is composed of a carbon/carbon composite material crucible base body and a composite ceramic layer attached to the inner surface of the carbon/carbon composite material crucible base body, the thickness of the composite ceramic layer is 1 mm-5 mm, and the composite ceramic layer is composed of the following components in percentage by mass: 50-70% of silicon carbide, 10-40% of boron nitride and 10-20% of silicon.
2. The method for preparing the carbon/carbon composite crucible with the composite ceramic layer according to claim 1, wherein in the step 1, the resin is selected from furan resin or phenolic resin, the particle size of the boron nitride is selected from 1 μm to 100 μm, and the particle size of the silicon powder is selected from 1 μm to 200 μm.
3. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 1, the pressure of hot-press molding is 0.2MPa to 0.8 MPa;
in the step 1, the overall size of the outer wall of the composite ceramic layer green body is 8-12% larger than that of the inner wall of the carbon/carbon composite material crucible base body, and the thickness of the composite ceramic layer green body is 1.2-6 mm.
4. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 1, the temperature of the carbonization treatment is 800-1000 ℃, and the treatment time is 1-3 h.
5. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 2, the resin is furan resin or phenolic resin, and the granularity of the silicon nitride is 1-50 μm;
in the step 2, in the binder, the mass fraction of the resin is 30-50%, and the mass fraction of the silicon nitride is 50-70%.
6. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 2, the density of the carbon/carbon composite material crucible matrix is 1.1g/cm3～1.4g/cm3The density of the carbon/carbon composite material crucible base body is 0.2g/cm3～0.6g/cm3The carbon fiber preform is densified by CVI deposition and/or resin impregnation.
7. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 2, the roughness Ra of the inner surface of the carbon/carbon composite material crucible base body is less than or equal to 1 mm.
8. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 2, the curing temperature is 160-220 ℃, and the curing time is 2-5 h; in the step 2, the temperature of the carbonization treatment is 800-1000 ℃, the time of the carbonization treatment is 0.5-2 h, and the temperature is reduced at the speed of less than or equal to 100 ℃/h after the carbonization treatment is finished.
9. The method for preparing a carbon/carbon composite crucible with a composite ceramic layer as claimed in claim 1, wherein: in the step 3, the granularity of the silicon powder is 0.001 mm-1 mm,
in the step 3, the temperature of the ceramic treatment is 1500-1800 ℃, and the heat preservation time is 30-90 min; the cooling rate is less than or equal to 170 ℃/h.
Priority Applications (1)
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